Method of producing novolaks



Nov. 4, 1952 H. BLQEM ETAL METHOD OF PRODUCING' NOVOLAKS F'iled March 1, 1951 2 SHEETS-SHEET 1 INVENTORS HERMAN BLOEM MARINUS STEL AGENT Nov. 4, 1952 OEM T A 2,616,872

METHOD OF PRODUCING NOVOLAKS Filed March 1, 1951 2 SHEETSSHEET 2 INVENTORS HERMAN BLOEM MARINUS STEL AGENT Patented Nov. 4, 1952 U NITE D FI-CSE METHOD 10F PRODUGING ;Novonms Herman Bloem an d Marinus Stel; Eindhoven,

Netherlands, assignors to "Hartford Natiohal Bank and Trust Company, flartford, Conn., as

trustee Application March 1, 195.1, SerialNo..2l3,4l2 In.theNetherlands March 14, 1950 4 Claims. (Cl. 260.15.4)

"Thisinvention reiates to methodsof producing, novolaksfrom phe nol anti formaldehyde withthe use of a catalyst. The term phenol is to be understood here to mean not oniy monohydroxybenzenegbut a1so suitable homologues thereof suoh as cresol and xylenol and polyvalent phenols, for example, resorcin. Such novolaks, which are not of themselves capable of solidifying, are usually produced by mixing in a reaction vessel measured quantities of .phenol and1formaldehyde together .with a catayst in a:suitable moleenlarratio andby causing them to-react, the phenol a1ways being present in excess. After the reaction, .the condensation produots are rembved from;the reactionvessel -and workedup. Formal dehyde is usually added as a solution in water. The catalyst may consist of acids or a1ka1is. Reaction maybe efiected in a continuous manner i. e.=a continuous stream of reaction components maybe supplied to a reaction apparatustoleave the latteras a.continuous stream of end-condensation product from .which the novolaks are btained byexpelling any water and catalyst.

It" has: been proposed to produce phenolf orma1- dehyde condensation products in .a continuous manner by.causinga stream of '1iqud, wherein phenol, forma1dehyde and catalyst -are :mixed in a desired ratio, t0 react whilst this mixture is passing througha tubularreaction vessel. However, =this and -similar methods, in which the condensation reaction is effected continuously in a Single reaction vessel, suffers from the limitation that gelatinisation often occurs as a result of which the contents of the apparatus become a gelatinizecl massandthe reactionis hence disturbed, more especialy if phenoland formalde- -siveiy with formaldehsrde, ;which mayinvolve an unduly high concentration of high-111016011131 eondensation products in the end-reaction product, thus causinggelatinisation. If the condensation reaotiontends to take place rapidly at the beginning of the-processand then gradualiymore s1ow1y, hichmaybe undesirable=in view-of a suitable distribution thereof over a number-of reacti on vessels, --the rate -of reaction is adjusted in eonnection wth the time during which the condensing mixture -stays in eaeh -reacton =ves sel suehthat the eendensation in each reaction vess e1 takesplace for-the desired part. In this case, gelatinisa-tioh will not occur if a sufiicient number of reaetion vessels is choseri inconnection withtheratio between -phenol and. formaldehyde.

The time of staying in a reacton vessel is to be -understooci -to mean in the steady state of theprocess, the ratio between the contentof the reaction vesse1 andthe volume supplied thereto per"unit time.

Asis known, therate of condgnsation depends both upon the nature ancl upon the concentration ofthecatalyst in-the c0ndensng mixture as well as uponthe temperatur.

"consequently,the condensation reaction may proceed ;at a constant temperature in a series of reaction vessels of equa1 size if the supply of catalyst to each vesselis ineasured such that a desred part of the condensation reacton takes p1aoe during a predetermned-stay in eaoh reaction-vessel. Alternatively, the catalyst together with the reaction components may pass successively through a11 reaction vessels and. by adjusting "the temperature of each individual react-ion vesselthecondensation;reaeton maytake plaeethereinfor the desired part.

A further alternatives to cause the reacting mixture to stay for a shorter or longer time in each indivdual reaction ;vessel by a suitable choice of the size of thereaction vesse1s.

..'hese methods of distributing the condensatien reacton pr0c.ess ver \a .number f r acti .vess.els;maviloe combned, foruexample, by dishufing thesllpply of cataiyst over several reaction vessels and by varyne he szeof th r maining reaction -vesselsso as to ensure the desr d dvison of the condensation r a n 1cenrdil1e;to the presnt invention, a method of producing novolaks in a continuous manner from.phenojl and formaldehydewith the use of a cata1yst, according to which a continupus stream of phenol and formaldehyde is introducedinto areacto n ta latio r m w.h.eh .th enficondensaton product is oarried, o ff contnuously, is characterized in that the reaction instalation oomprises a numberof series-connected reaction vessels through .whi ch th e r e actingiiquid mixture passes successivelygthe rate of condensaton of the reaction components being adjusted, in connecton with the time of staying in the reaction vessels, by adjustment of the temperature, of the catalyst concentration in each individual reaction vessel, by a suitable size of each individual reaction chamber or by a combination of these expedients, in such manner that the condensation reaction takes place for a desired part in each reaction vessel.

The optimum resu1t is obtained 1 oy causing the condensation reaction process to take place as evenly as possible, so thatan equal or approximately equal part of the condensation reaction takes place in each reaction vessel. In this case, in order to prevent gelatinisation, the number of reaction chambers may be smaller than 11 the reaction process were distributed arbitrarily over the reaction vesse1s.

The number of reaction vesse1s should, of

course, not be less than the minimum number required to prevent geiatinisaton. This depends upon the nature of the-phenol used and upon the ratio in which pheno1 and. formaldehyde react. When using a reacting mixture of monohydroxybenzene and formaldehyde combining with 0.70 mol. formaidehyde per mol. of added monohydroxybenzene, two reaction vessels are sufficient. If, however, 0.80 mol. formaldehyde isused per mol. monohydroxybenzene added, at least four reaction vesse1s are necessary, at 1east ten reaction vessels being requred if the. ratio is 1 to 0.86. When producing novolaks from a commercial creso1 mixture containing 50 to 55% by weight of metacresol in a molecular ratio of 1 mol. added creso1 to 0.70 mol. formaidehyde, eight reaction vesse1s are necessary.

In order that the production process may proceed expeditiously, it is essential that the reaction iiquid in each reaction vessel, partcularly if this liquid consists of two liquid phases, should be maintained in a suficiently mixed condition to prevent the resin from settling, e. g. by stirring. Furthermore, the reaction conditions should preferably not be a1tered during the process, so that stationary conditions are established in the reaction vessels, which means that the composition of a reaction mixture wi11 invariably be substantially the same at the same point in the installation and discrepancies in the final product are greatly reduced.

In order that the invention may be more clear- 1y understood and readily carried nto effect, it will now be described more fu1ly with reference to the accompa'nying dagrammatic drawings, given by way of example.

Example I Fig. 1 shows a test installation comprising uniform reaction vesse1s I to 5, the vessel I, wherein the agitator 8 provides suitable mixing, being shown in longitudinal section. The remaining reaction vessels 2 to5 also comprise agitators. If required, heating may be eiected by introducing steam into a double bottom 22. Vapours produced are condensed in the coo1ers 23 to 21. Inlet and out1et pipes for cooling water and 3I, respectvely, are provided. Through pipes the reaction vesse1s communicate with the open air.

From a supply vessel 9, 302ccs. of a solution containing 92 gms. of monbhydroxybenzene per 100 ccs. are caused to flow per hour into the reaction vessel I. From a similar supply vessel I0 198 ccs. of orma1in flow per hour into the reaction vessel I. The reaction vessels have a volume of 200 ccs. of which 135 ccs., i. e., the volume below the level of connecting pipe 33, are used efiectively. The vessels are heated to 98 C. and. their contents strred vigorously. Supp1y vessel II contains 0.29 n sulphuric acid which is passed through a distributing tube 32 to the reaction vessels I to 4 in quantities regulated by cocks I5 to I8, namely Ces. per hour To reaction vessel I 9.4 To reaction vessel 2 10 T0 reaction vessel 3 8.3 "I'o reaction vessel 4 9.3

The rates of flow from the vessels 9, III and I I are regulated by means of cocks I2, I3 and I4.

140 ccs. of 25% sulphuric acid flow per hour from a supp1y vessel 6 into reaction vessel 5, which quantity may be adjusted by a cock I9.

After steady conditions had been established in all the reaction vessels, it proved that in reaction vessel I 22% of the added formaldehyde had combned, in the vessel 2 14%, in vessel 3 18%, in vessel 4 26% and in vessel 5 12%. Of the added formaldehyde 8% did not combine, so that every 10 mol. phenol passed through the reaction apparatus were reacted with 7.9 mol. formaldehyde.

Example II Fig. 2 shows a test installation comprising supp1y vesse1s 9, I0 and II containing a resorcn solution containing 55.3 gms. of resorcin per 100 ccs. a formalin solution having a formaldehyde content of 39.6 gms. perl00ccs. and a 0.46 n potassium hydroxide solution, respectvely.

Of these solutions 415 ccs., 79.4 ccs. and 40.0 ccs., respectively flow per hour into reaction vessel I, which quantites ar regulated by means of cocks I2, I3 and I4. 'Ihis mixture, which reacts partly in the reaction vessel I, subsequently passes through the reaction vessels 2 and 3. In reaction vessel I, the temperature of the reacting mixture is adjusted to 43 C. by heating with the use of the double bottom. The temperatures of the second and third reaction vessels are adjusted to 60 C. and 98 C. respectively. After the stable conditions had been established in all the reaction vessels, the formaldehyde proved to have combined completely. This was also the case, if condensation took p1ace only in the third vessel, but then gelatinisation of the reaction mixture soon occurs.

Eccample III Three series-connected reaction vessels I to 3 in Fig. 3, which have an effective content of 30, 50 and ccs., respectively, are traversed, similarly as in Example II, by a reaction mixture initially composed of a resorcin solution having a resorcin content of 55.3 gms. per 100 ccs. from a supply vessel 9, formalin havng a formaldehyde content of 39.6 gms. per 100 ccs. from a supp1y vessel I0 and 2 n caustic soda solution from a supp1y vessel II, supplied in quantities of 342 ccs., 80 ccs. and 111 ccs. per hour, respectively, to a reaction vessel I the temperature of the reaction vessels being adjusted to 98 C.

In this manner, a resorcin novolak is obtained with the use of 6.2 mol. formaldehyde per 10 mol. resorcin. When this test was repeated, likewise with three reaction vesse1s but each having a content of 135 ccs. gelatinisation of the mixture soon occurred.

What we claim is: 1. A continuous process for preparing novolaks reacton vessel filled to a predetermined leve] with a.n intimate mixture of reaction components and reaction produets resultng from the reacton of the phenol, the formaldehyde, and the catalyst, cntnuously withdrawing a stream of the reaction mixture in the first vessel equal in volume to the streams of the reaction compcnents enterng the first vessel, continuously introducing the stream beng wthdrawn from the first vessel into a seconcl vessel filled with a reaction mixture in a more advanced stage of condensation, mxing the second stream with the reacton mixture in the second vessel, contnuously withdrawing a stream 01 the reaction mixture in the second. vessel equa1 in volume to the stream entering the second vessel, and successvely continuously introducing, mixing, and withdrawing equal vplumes of reaction mixtures in succeedng vessels until the reaction is substantially completed without gelatinzing the mixture in any vessel.

2. A process as claimed in claim 1 in which a stream of catalyst is ntroduced into the second REFERENCE S CIT ED The following references are of record in the file of this patent:

UNI'IED STATES PA'I'ENTS Number Name Date 1,660,403 Turkington Feb. 28, 1928 2,456,192 Houlton Dec. 14, 1948 OTHER REFERENCES Brothman: Chemical and Metallurgical Engineering, March 1943, pages 108-112. 

1. A CONTINUOUS PROCESS FOR PREPARING NOVOLAKS WHICH COMPRISES THE STEPS OF CONTINUOUSLY INTRODUCING STREAMS OF A PHENOL AND FORMALDEHYDE IN A PREDETERMINED RATIO AND A CATALYST INTO A FIRST REACTION VESSEL FILLED TO A PREDETERMINED LEVEL WITH AN INTIMATE MIXTURE OF REACTION COMPONENTS AND REACTION PRODUCTS RESULTING FROM THE REACTION OF THE PHENOL, THE FORMALDEHYDE, AND THE CATALYST, CONTINUOUSLY WITHDRAWING A STREAM OF THE REACTION MIXTURE IN THE FIRST VESSEL EQUAL IN VOLUME TO THE STREAMS OF THE REACTION COMPONENTS ENTERING THE FIRST VESSEL, CONTINUOUSLY INTRODUCING THE STREAM BEING WITHDRAWN FROM THE FIRST VESSEL INTO A SECOND VESSEL FILLED WITH A REACTION MIXTURE IN A MORE ADVANCED STAGE OF CONDENSATION, MIXING THE SECOND STREAM WITH THE REACTION MIXTURE IN THE SECOND VESSEL, CONTINUOUSLY WITHDRAWING A STREAM OF THE REACTION MIXTURE IN THE SECOND VESSEL EQUAL IN VOLUME TO THE STREAM ENTERING THE SECOND VESSEL, 